Properties of Gases

In order to describe or discuss the properties of gases we must know the variables which
determine the state of a gas. These variables are,
Pressure: The SI unit of pressure is the Paschal (Pa), but we commonly use other units. The
most common pressure units are: 1 atm = 101.325 kPa = 760 mmHg = 760 Torr.
Volume: The SI unit of volume is the m3. We will usually use the metric unit of volume the liter
(L), 1 L = 10-3 m3.
Temperature: The SI unit of temperature is the Kelvin. The Kelvin has the same size "degree"
as the Celsius scale, but the origin of the Kelvin scale is at absolute zero.
0o C = 273.15 K.
Temperature measurements for use in the gas laws will always be in Kelvin (K).

The Gas Laws: Mainly gas laws show how the variables, p, V, T, and n, are related to each other
in the description of gases.

Boyle's Law: Boyle found that, at constant temperature, the volume of the gas was inversely
proportional to the pressure on the gas. That is, at constant T,

.
We usually write Boyle's law in the form,

The latter form is useful when we think of p1 and V1 as the initial pressure and volume in an
experiment and p2 and V2 as the final pressure and volume.

Example calculation: A sample of gas has a volume of 4.60 L at sea level where the pressure is
1.00 atm. What would be the volume of the gas at an altitude of 20.0 km (about 12.4 miles)
where the pressure is 0.0553 atm if we keep the two temperatures the same?

Gay-Lussac's Law: The law is concerned with the behavior of gases at constant volume. That
is, how does the pressure depend on temperature if the volume is held constant. He found, by
experiment, that

In words, at constant volume the pressure of a gas is proportional to the absolute temperature.
(By the way, this kind of experiment is one way to determine that there is such a thing as an
absolute temperature. According to Gay-Lussac's law absolute zero is the temperature at which p
= 0.)

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Example calculation: A woman checks her tires in Tucson in June at 7:00 am in the morning
when the temperature is 68oF (20oC) and finds that the pressure is 35 psi. What is the pressure in
her tires when she is driving through Phoenix with the temperature at 113oF? (Hint: one
atmosphere is approximately 14.7 psi.)
Charles' Law: Charles was studying the properties of gases at constant pressure. He found that,

(This is another equation that suggests that there is an absolute zero of temperature. The absolute
zero is the temperature at which the pressure of the gas would go to zero.)
Example problem: A sample of gas has a volume of 20.6 L at 25.0oC. At what temperature
would the volume double if the pressure is held constant?
The Combined Gas Law: If we multiply Boyle's law, Gay-Lussac's law and Charles' law
together and take the square root we arrive at the combined gas law,

That is, for a given sample of gas

This equation allows us to do calculations in which two variables change at the same time.
Example problem1: A sample of gas has a volume of 22.4 L at a pressure of 1.00 atm and
0.0oC. What is the volume at 0.500 atm and 100.oC?
Example problem2:For instance, suppose you had a gas at 15.0 atm pressure, at a volume of
25.0 L and a temperature of 300 K. What would the volume of the gas be at standard temperature
and pressure? Standard pressure is 1.00 atm and standard temperature is 0 oC (or 273 K). Set up a
table of knowns and unknown, as before:

Substitute these variables into the combined gas law. Since the moles are unchanged, the mole
terms have dropped out of the equation:

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Solve the volume, V2. Multiply both sides of the equation by 273 K and divide both sides of the
equation by 1.00 atm:

Gay-Lussac's Law of Combining Volumes

Gay-Lussac conducted other experiments on gases, in particular, on the volumes of gases
involved in chemical reactions.
He found that the ratio of the volumes of gases involved in chemical reactions (at the same
temperature and pressure) were always simple fractions (fractions composed of small whole
numbers).
For example, in the reaction
N2(g) + 3 H2(g) 2 NH3(g),
at constant temperature and pressure, Gay-Lussac found that the ratio of the volume of H2(g) to
the volume of N2(g) was always 3 to 1, regardless of the initial volumes used. Likewise, the ratio
of the volume of H2(g) to the volume of NH3(g) was always 3 to 2.
This lead Avogadro to postulate ,

Avogadro's Law: Avogadro's law states that, at the same temperature and pressure, equal
volumes of gases contain the same number of molecules. This law provides an explanation for
why Gay-Lussac's law of combining volumes works.

The Ideal Gas Law

Going back to the combined gas law

it was easily seen that from experiments that the constant in this equation depended on the
quantity of gas. In fact, the constant is proportional to the number of moles, n, of gas. If we call
the proportionality constant R, we get

The latter of these two equations is known as the ideal gas law. (A more accurate name for this
equation would be "the ideal gas equation of state." That is because it provides a relationship
between the state variables p, V, T, and n. We can't pick arbitrary values for these four variables.
If we select the values of any three variables the fourth is fixed by the equation.)
It is easy to see that the ideal gas law contains all of the gas laws we have already discussed. It
also contains some that we have not discussed.

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For example: In Boyle's law temperature is held constant. If take the ideal gas law and keep all
the constant quantities (n, R, and T) on the right-hand side and all the variable quantities (p and
V) on the left-hand side we get Boyle's law,

To get the combined gas law, leave the constants (n and R) on the right-hand side and move T to
the left-hand side with the other variables, p and V, to get

which is the combined gas law.

The constant R is called the "gas constant," or sometimes the "universal gas constant." It is
expressed is several different set of units.
R = 0.0820578 Latm/Kmol
= 0.0831451 Lbar/Kmol
= 8.31451 J/Kmol.
In this course we will mostly use R = 0.082578 Latm/Kmol.

Standard Temperature and Pressure (STP)

It is very common to define 0oC and 1 atm pressure as standard temperature and pressure,
abbreviated "STP."
The reason for this is that it doesn't make any sense to compare volumes of gases unless the
gases being compared are at the same temperature and pressure.
The volume of 1.00 mol of an ideal gas at STP is easy to calculate to be 22.4 L.

Stoichiometry of Gases
We can do stoichiometry with gases. We use the same "road map" as in our previous
stoichiometry problems. We just have to add our method for going from volumes to moles,
namely,

The rest of the stoichiometric calculation is the same as before. For example, we use the same
"reaction fraction."

Gas Mixtures, Partial Pressures, and Dalton's Law

In a mixture of gases we speak of the total pressure of the gas mixture and the "partial pressures"
of the individual gases in the mixture.
The partial pressure of a gas in a mixture is defined as the pressure the gas would have (at the
same temperature and in the same volume) if all the other component gases were removed
leaving only the one gas.
For example, consider a sealed box containing air. Air is a mixture of gases containing mostly N2
and O2, with a little bit of Ar, CO2, some water vapor, and traces of other gases like He, Ne, H2S,
etc.

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Dalton's law of partial pressures says that the total pressure of a gas mixture is the sum of all the
partial pressures of all the gases in the mixture. If we number the gases as gas 1, gas 2, gas 3, and
so on then,
p = p1 + p2 + p3 + . . . .
We can derive Dalton's law from the ideal g as law. Note that the n in

doesn't have any information about the identity of the gas and the equation is the same regardless
of the identity of the gas. There is no reason why n couldn't be the sum of the number moles of
each component in a gas mixture.
That is,
n = n1 + n2 + n3 + . . . .
If we place this n into the ideal gas law we get,

which is Dalton's law.

Example: What is the total pressure of a mixture of He and O2 where the partial pressures are
0.800 atm and 0.198 atm respectively?

Kinetic Molecular Theory of Gases

The kinetic molecular theory of gases is an example of model building. That is, we build a
(theoretical) model of how we think nature operates and then calculate the properties of our
model to see how they compare with nature.
If the properties of our model agree with what we see in nature we keep the model and try to
improve it. If the properties of our model do not agree with nature we throw it away (or make
drastic revisions).
The model: Our model of a gas contains
N molecules
of mass, m,
in a volume V,
at temperature, T.

•An explanation of what happens at the molecular level that causes the observations in the ideal
gas laws.
Postulates of Kinetic Molecular Theory
1. Gases consist of large numbers of molecules in continuous random motion
2. The volume of all the molecules of gas is negligible compared to the total volume (i.e.,
each gas molecule is basically an infintessimallysmall dot).
3. Attractive and repulsive forces between molecules are negligible.
4. Energy transitions between molecules are perfectly elastic. The average kinetic energy of
the molecules will not change over time as long as the temperature stays constant.

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 5. The absolute temperature is proportional to the average kinetic energy of the gas. At any
given temperature all gases in the mixture have the same average kinetic energy.
 KE = ½ mu2; u = the root mean square (rms) speed of the gas. (root mean square is an
averaging technique, though it is not the same as the average)

The kinetic theory explains the gas law: Important observations:

 volume increases at constant temperature (Boyle’s law). Molecules must travel further to
reach the wall of a larger container. Thus, collisions against the container wall are less
frequent, the pressure therefore drops.
 Temperature increases at constant volume (Charles’ Law). when temperature (and kinetic
energy) increase, the speed of the molecules increases. Faster molecules collide with the
container walls more often, so pressure increases.

The kinetic energy for N molecules is N times the kinetic energy for one molecule,

These equations provide a lot of information. For example we can calculate the average velocity
of a molecule with

Notice that the average velocity is proportional to the square root of the temperature and to the
inverse of the square root of the mass of the molecule. We will use this latter fact when we talk
about diffusion.
In calculating the average speed it is easier to use the formula weight of the molecules than mass
of one molecule. Remembering that

,
we can rewrite the expression for average velocity as

.
The only thing we have to be careful about here is the make sure the formula weight is expressed
in kg/mol instead of g/mol. R, of course, must be in SI units, namely 8.31451 J/K mol.
Example, calculate the average velocity of a N2 molecule at room temperature, 298 K.

Diffusion: If we release a small amount of ammonia gas in a quiet room (no air currents or
turbulence or mixing) the ammonia will eventually spread throughout the room, due to the
motion of the molecules.
Looking at our equation for average molecular velocities we see that the average speed is
inversely proportional to the square root of the formula weight. In equation form,

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 .
The rate at which a molecule diffuses through another gas is proportional to its average velocity.
Thus the diffusion rate is inversely proportional to the square root of the formula weight.
We will not need to know how to calculate absolute diffusion rates in this course, but we will
need to be able to calculate relative diffusion rates. The ratio of the diffusion rate of gas A
(RateA) to the diffusion rate of gas B (RateB) is, from the above discussion,

Example: Calculate how much faster He will diffuse than oxygen gas at 298 K.
Diffusion: Diffusion is the movement of one gas through another gas when there is no
convection, turbulence, or other currents or mixing. The rate of diffusion is proportional to the
average velocity of the molecules.
Looking at our equation for average molecular velocities we see that the average velocity is
inversely proportional to the square root of the formula weight. In equation form,

.
We will not need to know how to calculate absolute diffusion rates in this course, but we will
need to be able to calculate relative diffusion rates. The ratio of the diffusion rate of gas A
(Diffusion RateA) to the diffusion rate of gas B (Diffusion RateB) is, from the above discussion,

Example: Calculate how much faster He will diffuse than oxygen gas at 298 K.

Effusion: Effusion is another word for leakage. Gases tend to leak out of containers, either
through simple "pin holes," or through pores in the material of the container. For example,
balloons filled with He gas tend to lose helium because the rubber of the balloon has tiny pores
thorough which the helium can leak out. (Most party stores now sell balloons make of a mylar
film because mylar has much smaller pores and the helium "effuses" out much slower. Effusion
follows the same equation for relative effusion rates as diffusion,

Real Gases (Nonideal Gases)

The ideal gas equation of state can be derived from the two assumptions that there are no
intermolecular forces between the molecules and that the molecules are "point masses," that is,
the molecules have no size. Neither of these assumptions is correct, although they are both
approximately correct if the pressure is low and the temperature is high.
 Assumptions in kinetic theory of gases not always valid.
 Molecules are not infinitely small
 Attractive and repulsive forces are notnegligible.

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  Collisions are notalways elastic.
Deviations more likely to occur at…
•low temperature: Molecules moving slower, intermolecular forces become a greater factor
(especially near liquid/gas interface).
•Higher pressure: Molecule size becomes an greater factor; interfering with travel of molecules.
•Corrections to ideal gas equation are made to take this into account.
–Van derWaal’sequation is one example
So far we have only considered the behavior of "ideal" Gases. How does a real gas differ from an
ideal gas? Recall that an ideal gas is considered to be a point mass -- a particle so small that the
volume of that particle is negligible. A real gas particle does have real volume. For an ideal gas,
the collisions between gas particles was said to be "elastic" -- no attractive or repulsive forces
exist, and thus, no energy is exchanged during collisions. For a real gas, collisions are non-
elastic. There are a number of real gas laws. We will look at only one here, the van der Waal's
equation:

Johannes van der Waals found a way to correct for both of these assumptions. He put in two new
terms. One of the terms corrects for the actual size of the molecules. He wrote V nb in place of
the volume, V. The nb term takes account of the fact that one molecule can't freely roam around
the entire volume, V. It is excluded from portions of the volume which are occupied by other
molecules. The parameter, b, is the "excluded volume" due to one mole of particles.
Also, the physical pressure felt by a molecule is larger than the pressure produced by the walls of
the container. This is because the particles attract each other and so tend to draw molecules on
the edge of the gas into the bulk gas. He added a term, an2/V2, to correct for this extra pressure.
The van der Waals equation of state is then given by,

The parameters, a and b, are called the "van der Waals parameters." They are different for
different gases.
Notice how "corrections" are being made to the pressure term and the volume term. Since
collisions of real Gases are non-elastic, the term n2a/V2 is correcting for the interactions of these
particles. The value of a is a constant, and must be experimentally determined for each gas. Since
real gas particles have real volume, the nb term is correcting for the excluded volume. The value
of b is a constant, and must be determined experimentally for each gas. The van der Waals
constants, a and b for many gases have been tabulated. Begin by dividing both sides of the
equation by the volume term, V - nb:

Next, subtract the interparticle interaction term, n2a/V2 from both sides of the equation:

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Using the real gas law, let's find the pressure of 2.00 moles of carbon dioxide gas at 298 K in a
5.00 L container. The van der Waals constants for carbon dioxide are: a = 3.592 L2. atm/mol2 and
b = 0.04267 L/mol.
Substituting all of the variables into the appropriate terms of the equation, one obtains the
pressure of :

Compare this to the pressure calculated using the ideal gas law:

Maxwell Boltzmann Distribution

All the molecules of a particular chemical, compound or element have the same mass, so their
kinetic energy is only dependent on the speed of the particles.
Remember Kinetic Energy = ½mv2
In any particular mixture of moving molecules, the speed will vary a great deal, from very slow
particles (low energy) to very fast particles (high energy). Most of the particles however will be
moving at a speed very close to the average.
The Maxwell-Boltzmann distribution shows how the speeds (and hence the energies) of a
mixture of moving particles varies at a particular temperature.
Kinetic Energy Distribution
When we move from the world of the atom to the world we occupy we must recognize that we
are dealing with huge numbers of atoms and molecules, not just one or two. With these huge
numbers we are forced to rely on statistics since there is no longer any way that we can calculate
the behavior and interactions of all of the molecules in even a very small collection. Ludwig
Boltzmann and James Clerk Maxwell contributed to the science of statistical thermodynamics in
which we examine the properties of very large numbers of molecules. While we recognize that
we can't predict the behavior of any one molecule with any precision, we can quite exactly
predict the behaviour of large quantities of molecules.
We know that the kinetic energy of an atom or molecule is calculated by the formula:
ke = 1/2 mv2
where m is the mass of the particle and v is its velocity.
When we have to describe the distribution of kinetic energies in a large collection of atoms or
molecules, we must resort to statistics. Maxwell and Boltzmann discovered that this distribution
may be described by plotting the fraction of molecules in a container with a given kinetic energy
vs kinetic energy.

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Notice that the plot is not symmetrical so the most probable speed is not the same as the average
speed.

Effect of temperature
Temperature is directly proportional to the average kinetic energy of molecules, and, in fact, the
equation:
ke = 3/2 nRT
where n is the number of moles of gas, T is the temperature in Kelvins, and R is the Universal
gas constant
If T is proportional to the average kinetic energy, then we'd expect for this change in the average
kinetic energy to be reflected in changes in the shape of the Boltzmann distribution. Since in our
example we're using probability on the vertical axis, the area under the curve must be exactly
equal to 1.0 at all times (there must be a unit probability of the gas having some kinetic energy).
As temperature increases, the curve will spread to the right and the value of the most probable
kinetic energy will decrease. This is illustrated below for several temperatures.

It is often useful to fix our attention on some value of the kinetic energy and ask what happens to
the fraction of molecules with kinetic energies equal to or greater than this value as we change
the temperature. Let's re-examine the curves from above with this in mind. These curves are
illustrated below. I have selected a reference kinetic energy in Red. Notice that as T increases,
the fraction of molecules with energies greater than the red line increase. This fact is of

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fundamental importance to properties of matter such as vapro pressures, and we will see that
these ideas underlie the effect of temperature on the rates of chemical processes. Whenever a
question arises about the effect of temperature on some chemical process, you should refer back
to the Maxwell-Boltzmann concepts.

In any particular mixture of moving molecules, the speed will vary a great deal, from very slow
particles (low energy) to very fast particles (high energy). Most of the particles however will be
moving at a speed very close to the average.
The Maxwell-Boltzmann distribution shows how the speeds (and hence the energies) of a
mixture of moving particles varies at a particular temperature.

Points to notice:
No molecules at zero energy
Few molecules at high energy
No maximum energy value
For the reaction to occur, the particles involved need a minimum amount of energy - the
Activation energy (EACT). If a particle is not in the shaded area, then it will not have the required
energy so it will not be able to participate in the reaction.

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